US8604093B2 - Fire-resistant polyurethane foam and fabrication method thereof - Google Patents

Fire-resistant polyurethane foam and fabrication method thereof Download PDF

Info

Publication number
US8604093B2
US8604093B2 US12/900,478 US90047810A US8604093B2 US 8604093 B2 US8604093 B2 US 8604093B2 US 90047810 A US90047810 A US 90047810A US 8604093 B2 US8604093 B2 US 8604093B2
Authority
US
United States
Prior art keywords
fire retardant
fire
hydroxyl
premixture
polyurethane foam
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US12/900,478
Other versions
US20110124760A1 (en
Inventor
Po-Ju Chen
Sung-Jeng Jong
Ren-Kuen Chang
Chin-Shang Hsu
Jer-Young Chen
Yih-Her Chang
Chei Kao
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Industrial Technology Research Institute ITRI
Original Assignee
Industrial Technology Research Institute ITRI
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Industrial Technology Research Institute ITRI filed Critical Industrial Technology Research Institute ITRI
Assigned to INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE reassignment INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHANG, YIH-HER, CHEN, JER-YOUNG, JONG, SUNG-JENG, CHANG, REN-KUEN, CHEN, PO-JU, HSU, CHIN-SHANG, KAO, CHEI
Publication of US20110124760A1 publication Critical patent/US20110124760A1/en
Priority to US14/073,805 priority Critical patent/US8865782B2/en
Application granted granted Critical
Publication of US8604093B2 publication Critical patent/US8604093B2/en
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066Use of inorganic compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/38Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016Flame-proofing or flame-retarding additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00Manufacture of cellular products

Definitions

  • FIG. 6 is a schematic view showing the combination of different particle sizes for an inorganic fire retardant
  • a flame test was conducted on the foam by a gas torch (burner diameter: 1.5 inches) with a flame temperature of 950° C., during which the backside temperature of the foam was measured, wherein the results are shown in FIG. 8 .
  • the thickness of the foam shrunk from 4 cm to 3.8 cm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

A fire-resistant polyurethane foam is provided. A hydroxyl-containing inorganic fire retardant is premixed with a polyisocyanate and a polyol, respectively, to form two premixtures. Then, the two premixtures are mixed for reaction to form a fire-resistant polyurethane foam. Preferably, a combination of different particle sizes of the fire retardant is employed to maximize the amount of the fire retardant and increase the fire resistance of the foam.

Description

CROSS REFERENCE TO RELATED APPLICATIONS
This application claims priority of Taiwan Patent Application No. 098139458, filed on Nov. 20, 2009, the entirety of which is incorporated by reference herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a polyurethane (PU) foam, and in particular relates to a low-density, fire-resistant polyurethane foam and a fabrication method thereof.
2. Description of the Related Art
Fire-resistant construction materials are classified into three groups: inorganic fiber board, inorganic fiber cotton, and organic fire-retardant foam. Inorganic fiber board is relatively heavy and has a fixed shape which restricts its use and the thermal insulation is unsatisfactory. Inorganic fiber cotton has superior fire resistance and thermal insulation, but has no mechanical strength. Organic fire-retardant foam, such as phenolic foam, is light and has good thermal insulation. However, organic foam generally has poor fire resistance, and tends to shrink and gasify under exposure to flames.
A polyurethane foam incorporated with inorganic fire retardant combines the advantages of organic and inorganic materials, which are, high processability, light-weight, and high thermal insulation for organic materials and excellent fire resistance for an inorganic materials. However, in the conventional art, an inorganic fire retardant is merely physically blended in polyurethane, exhibiting limited improvement in fire resistance. Furthermore, the additional amount of the inorganic fire retardant has restriction. For example, the maximum permissible amount for a 1 μm aluminum hydroxide in polyurethane is only 36.5 wt % (based on the total weight of the fire resistant foam). If the amount exceeds the value, the resulting mixture would not be processable due to unusually high viscosity.
FIG. 1 illustrates a fabrication scheme of a fire-resistant polyurethane foam disclosed by Canadian Patent No. 1222599A1 and U.S. Pat. No. 4,317,889, wherein a fire retardant is first added to a polyol, which is then mixed with a polyisocyanate to cause a foaming reaction. Because the fire retardant is only present in the polyol, the amount of the fire retardant (and therefore the fire resistance) is limited by the volume of the polyol solution.
FIG. 2 illustrates another fabrication scheme of a fire-resistant polyurethane foam disclosed by U.S. Pat. No. 6,010,565 and GB 1472245, wherein a fire retardant, a polyisocyanate, and a polyol are mixed together simultaneously. Because the contact of the polyisocyanate and the polyol initiates the foaming reaction immediately, it is not possible to incorporate a large amount of the fire retardant in such a short period.
FIG. 3 illustrates a further fabrication scheme of a fire-resistant polyurethane foam disclosed by GB 1499168 and EP0308769B1, wherein an open-cell polyurethane foam is impregnated with a cross-linkable latex solution including aluminum hydroxide.
It should be noted that the conventional art uses a single particle size for the inorganic fire retardant. None of the above cited references address the effect of using inorganic fire retardants having different particle sizes.
BRIEF SUMMARY OF THE INVENTION
According to one aspect of the invention, a method for fabricating a fire-resistant polyurethane foam is provided, which comprises premixing a polyisocyanate and a hydroxyl-containing inorganic fire retardant to form a first premixture, wherein the polyisocyanate reacts with the hydroxyl-containing inorganic fire retardant to form a chemical bond; premixing a polyol, a blowing agent, and the hydroxyl-containing inorganic fire retardant to form a second premixture; and mixing the first premixture and the second premixture to proceed with a foaming reaction to obtain a fire-resistant polyurethane foam.
According to another aspect of the invention, a fire-resistant polyurethane foam is provided, which comprises a polyurethane; about 50-80 wt % of a hydroxyl-containing inorganic fire retardant, based on the weight of the fire-resistant polyurethane foam, wherein the hydroxyl-containing inorganic fire retardant reacts with the polyurethane to form a chemical bond; wherein the fire-resistant polyurethane foam has a density of about 0.05-0.7 g/cm3.
A detailed description is given in the following embodiments with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention can be more fully understood by reading the subsequent detailed description and examples with references made to the accompanying drawings, wherein:
FIGS. 1-3 illustrate three conventional fabrication schemes of a fire-resistant polyurethane foam;
FIG. 4 illustrates a fabrication scheme of a fire-resistant polyurethane foam according to an embodiment of the invention;
FIG. 5 is a schematic view showing the use of a single particle size for an inorganic fire retardant;
FIG. 6 is a schematic view showing the combination of different particle sizes for an inorganic fire retardant;
FIG. 7 is a diagram showing the backside temperature of the foams of Example 1 and Comparative Example 1 as a function of heating time;
FIG. 8 is a diagram showing the backside temperature of the foam of Example 2 as a function of heating time; and
FIG. 9 is a diagram showing the backside temperature of the foams of Comparative Examples 3-5 as a function of heating time.
DETAILED DESCRIPTION OF THE INVENTION
The following description is of the best-contemplated mode of carrying out the invention. This description is made for the purpose of illustrating the general principles of the invention and should not be taken in a limiting sense. The scope of the invention is best determined by reference to the appended claims.
Embodiments of the invention provide a low-density, low-cost, high-strength, high-thermal insulation fire resistant foam by taking advantages of the low density of polyurethane foam and the fire resistance of inorganic fire retardants. In preferred embodiments, the fire-resistant foam is capable of withstanding flame temperatures of about 1000° C. for more than 1 hour without losing its structural integrity, which effectively prevents direct heat transfer (to the interior materials or objects).
FIG. 4 illustrates a fabrication scheme of a fire-resistant polyurethane foam according to an embodiment of the invention. As shown, to maximize the additional amount of inorganic fire retardant to improve fire resistance, a hydroxyl-containing inorganic fire retardant (e.g., aluminum hydroxide) is premixed with a polyisocyanate and a polyol, respectively, to form two premixtures. Then, the two premixtures are mixed for reaction to form a fire-resistant polyurethane foam. As such, the amount of inorganic fire retardant can be significantly increased to above 40 wt %, or preferably about 50-80 wt %.
According to an important feature of the invention, during the premixing procedure with polyisocyanate, the hydroxyl group of the fire retardant will react with the isocyanate (—NCO) group of the polyisocyanate; thereby increasing the permissible additional amount of the fire retardant. Moreover, the reaction forms a chemical bond between the fire retardant and the polyurethane; thus strengthening structural integrity of the composite. The resulting fire-resistant foam does not melt, shrink or produce flaming drops under exposure to flame or ignition sources.
Meanwhile, in the conventional fabrication schemes of FIGS. 1-2, since the reaction between polyisocyanate and polyol is much faster than the reaction between polyisocyanate and aluminum hydroxide, polyisocyanate will first react with polyol before it has the chance to react with aluminum hydroxide. As a result, the conventional foam is likely to shrink and produce flaming drops under exposure to flame. In the conventional fabrication scheme of FIG. 3, aluminum hydroxide is only physically coated on the outer surface of polyurethane (without chemical bonding), which necessitates an additional process step and its structural integrity of the foam is not increased thereby.
According to another important feature of the invention, a combination of different particle sizes of the fire retardant is employed to maximize the amount of the fire retardant and increase the fire resistance of the foam. A smaller fire retardant particle can result in an abrupt increase of viscosity when added to the polyurethane reaction mixture due to the larger surface area, and therefore its additional amount is rather limited. Meanwhile, a larger fire retardant particle allows a greater additional amount, but the fire resistance is relatively poor. A combination of different particle sizes of the fire retardant can maximize the amount of the fire retardant without sacrificing the fire resistance.
Referring to FIGS. 5-6, FIG. 5 shows the use of an inorganic fire retardant 10 a having a single particle size, while FIG. 6 shows the use of inorganic fire retardants 10 a, 10 b, 10 c having different particle sizes. It can be seen that the combination of different particle sizes can fill up a given space more efficiently; thereby increasing the additional amount.
In the following, details of the fabrication method and composition of the fire-resistant polyurethane foam will be described.
The polyisocyanate suitable for use herein is a compound having two or more isocyanate groups per molecule, including but not limited to: aromatic polyisocyanates, aliphatic polyisocyanates, cycloaliphatic polyisocyanates, heterocyclic polyisocyanates, and so on. A mixture of the above is also suitable for use. The polyisocyanate preferably has an NCO content of about 5-50 wt %. Representative examples of the polyisocyanate include: toluene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′-dicyclohexylmethane diisocyanate (H12MDI), p-phenylene diisocyanate (PPDI), and (p,p′-bisphenyl diisocyanate (BPDI).
The polyol suitable for use herein is a polyol having two more active groups, including polyether polyols and polyester polyols. Representative examples of the polyol include: poly(butanediol-co-adipate) glycol (PBA), polytetramethylene glycol (PTMEG), Poly(hexanediol-co-adipate) glycol (PHA), poly(ethylene-co-adipate) glycol (PEA), polypropylene glycol, and polyethylene glycol. The polyol may have a number average molecular weight ranging from about 200 to about 6000, or preferably from about 600 to about 3000. The above polyols are used either alone or in combination.
The polyol is first mixed with a blowing agent, a catalyst and a dispersing agent, followed by addition of a fire retardant to proceed with premixing. Water is the most commonly used blowing agent for polyurethane. The catalyst suitable for use herein includes metallic compounds and tertiary amines, wherein the metallic compounds are, for example, dibutyltin dilaurate (T-12), stannous octoate (T-9), and stannous oleate, and the tertiary amines are, for example, triethylenediamine, triethylamine, tripropylamine, N-ethyl morpholine, and N,N-dimethyl cyclohexanamine. The dispersing agent suitable for use herein includes Disperbyk series manufactured by BYK Chemie. In a specific embodiment, the blowing agent, the catalyst, and the dispersing agent may be present in amounts of 1 wt %, 0.1 wt %, and 2.5 wt %, respectively, based on the weight of the polyol. It will be appreciated, however, the other ratios may be used.
The hydroxyl-containing inorganic fire retardant which is suitably used herein includes, but is not limited to, aluminum hydroxide, magnesium hydroxide, silicon oxide, titanium oxide, calcium carbonate, or combinations thereof, wherein aluminum hydroxide and magnesium hydroxide are particularly preferred. The fire retardant may inherently have the hydroxyl group or have the hydroxyl group after surface modification. The hydroxyl-containing inorganic fire retardant may have a particle size ranging from about 0.5 μm to about 100 μm. Preferably, a combination of two or more different particle sizes is employed to maximize the amount of the fire retardant and increase the fire resistance. It should be noted that, however, using a fire retardant of a single particle size is permissible in the invention. In a specific embodiment, a combination of particles sizes of 0.5-5 μm, 5-20 μm, and 20-100 μm in a weight ratio of 1:0.1-2:0.1-2, or preferably 3:2:4, is employed. The hydroxyl-containing inorganic fire retardant may be present in an amount of about 50-80 wt %, based on the total weight of the fire-resistant polyurethane foam. The weight ratio of the fire retardant in the polyisocyanate premixture to the fire retardant in the polyol premixture is about 1:9 to about 9:1, or preferably about 1.5:1.
In addition to the hydroxyl-containing inorganic fire retardant, other fire retardants may be optionally used. For example, the fire-resistant polyurethane foam may further contain 0-10 wt % of a phosphorus-containing fire retardant (such as ammonium polyphosphate), 0-5 wt % of a nitrogen-containing fire retardant (such as melamine), 0-5 wt % of a carbonization agent (such as pentaerythritol), and 0-15 wt % of a glass fiber (such as short glass fiber), based on the total weight of the fire-resistant polyurethane foam. The above fire retardants may be premixed with the hydroxyl-containing inorganic fire retardant and then added to the polyisocyanate or polyol.
According to the fabrication method of the invention, the hydroxyl-containing inorganic fire retardant is premixed with a polyisocyanate and a polyol, respectively, to form two premixtures. The premixing can be carried out at a mixing speed of about 100-400 rpm for a period of about 5-30 minutes to insure a thorough mixing. Thereafter, the two premixtures are mixed at a higher speed, for example, about 1000-3000 rpm for a period of about 5-30 seconds. The resulting mixture is then placed into a mold to proceed with the foaming process. The fire-resistant polyurethane foam thus obtained may have a density of about 0.05-0.7 g/cm3. In preferred embodiments, the fire-resistant polyurethane foam is capable of withstanding flame temperature of about 1000° C. for more than 1 hour without losing its structural integrity; effectively preventing direct heat transfer to the interior.
EXAMPLES
Materials
a. polyisocyanate: UR-398B (polymeric MDI) from KUANG LUNG SHING CORPORATION
b. polyol: UR-398A from Kuang Lung Shing Corp.
c. dispersing agent: 2280 from Marvel Chemical
d. dispersing agent: Disperbyk-110 from BYK Chemie
e. catalyst: T-12 (dibutyltin dilaurate)
f. catalyst: DABCO 33-LV (triethylenediamine solution) from Air Products and Chemicals.
g. aluminum hydroxide: H-42M (particle size: 1 μm) from Showa Denko K.K.
h. aluminum hydroxide: H-32 (particle size: 8 μm) from Showa Denko K.K.
i. aluminum hydroxide: H-10 (particle size: 55 μm) from Showa Denko K.K.
j. nitrogen-containing fire retardant: melamine
k. phosphorus-containing fire retardant: ammonium polyphosphate
l. carbonization agent: pentaerythritol
m. short glass fiber: 202P 3.2 from Taiwan Glass Inc.
n. “MIA4”: denotes a mixture of melamine, ammonium polyphosphate, and pentaerythritol in a weight ratio of 3:16:1.
In the following examples and comparative examples, all percentages are by weight unless otherwise specified.
Example 1
The ingredients and amounts thereof given in Table 1 were dried mixed to provide Fire Retardant Powder C. The ingredients and amounts thereof given in Table 2 were thoroughly mixed to provide Liquid A. 116.2 g of the Fire Retardant Powder C was added to 68.7 g of polyisocyanate (UR398B, Liquid B) and thoroughly mixed at a speed of 250 rpm for 7 minutes; thus, providing a first premixture. Meanwhile, 65.2 g of the Fire Retardant Powder C was added to Liquid A and thoroughly mixed at a speed of 250 rpm for 7 minutes; thus, providing a second premixture. The first and second premixtures were mixed at a speed of 1200 rpm for about 10 seconds, and then placed into a mold to proceed with the foaming process. A 10 cm*20 cm*4 cm foam with a density of 0.335 g/cm3 was obtained, which contained 60.2% of the fire retardant.
TABLE 1
weight (g)
Al(OH)3 (H-42M) 32.7
Al(OH)3 (H-32) 21.8
Al(OH)3 (H-10) 43.7
MIA4 10.9
TABLE 2
weight (g)
Polyol (UR398A) 45.8
Dispersing agent 2.17
(2280)
Dispersing agent 0.58
(Disperbyk-110)
Comparative Example 1
The ingredients and amounts thereof given in Table 3 were dried mixed to provide Fire Retardant Powder D. All of the Fire Retardant Powder D was added to 68.7 g of polyisocyanate (UR398B, Liquid B) and thoroughly mixed at a speed of 250 rpm for 7 minutes to provide a premixture. Thereafter, the premixture and the Liquid A as in the Example 1 were mixed at a speed of 1200 rpm for about 10 seconds, and then placed into a mold to proceed with the foaming process. A 10 cm*20 cm*4 cm foam with a density of 0.339 g/cm3 was obtained. The fire retardant present in the foam was 36.5%, which was the maximum amount permissible for processing.
TABLE 3
weight (g)
Al(OH)3 (H-42M) 20.2
Al(OH)3 (H-32) 13.5
Al(OH)3 (H-10) 27
MIA4 6.7
Comparative Example 2
The Fire Retardant Powder C, Liquid A, and Liquid B as in the Example 1 were mixed simultaneously at a speed of 1200 rpm for about 10 seconds. As a result, the Fire Retardant Powder C could not be uniformly dispersed in the liquid mixture and lumps caused by aggregation of powers were observed; making it impossible to introduce the reaction mixture into a mold to proceed with the foaming process. In addition, since the mixing of Liquid A and Liquid B promptly initiated the foaming process, it was impossible to fully disperse the fire retardant powder by increasing the mixing time.
Flame Test
A flame test was conducted on the foams obtained in the Example 1 and Comparative Example 1 by a gas torch (burner diameter: 1.5 inches) with a flame temperature of 950° C., during which the backside temperature of the foams was measured, wherein the results are shown in FIG. 7. The foam of the Example 1 was capable of withstanding the flame temperature for more than 1 hour and maintaining its structural integrity, while the foam of the Comparative Example 1 lost its structural integrity in less than 20 minutes due to cracking.
Example 2
The ingredients and amounts thereof given in Table 4 were dried mixed to provide Fire Retardant Powder E. The ingredients and amounts thereof given in Table 5 were thoroughly mixed to provide Liquid F. 86 g of the Fire Retardant Powder E was added to 50.9 g of polyisocyanate (UR398B, Liquid B) and thoroughly mixed at a speed of 250 rpm for 7 minutes; thus, providing a first premixture. Meanwhile, 48.3 g of the Fire Retardant Powder E was added to Liquid F and thoroughly mixed at a speed of 250 rpm for 7 minutes; thus, providing a second premixture. The first and second premixtures were mixed at a speed of 1200 rpm for about 10 seconds, and then placed into a mold to proceed with the foaming process. A 10 cm*20 cm*4 cm foam with a density of 0.27 g/cm3 was obtained.
A flame test was conducted on the foam by a gas torch (burner diameter: 1.5 inches) with a flame temperature of 950° C., during which the backside temperature of the foam was measured, wherein the results are shown in FIG. 8. After the flame test, the thickness of the foam shrunk from 4 cm to 3.8 cm.
TABLE 4
weight (g)
Al(OH)3 (H-42M) 37.4
Al(OH)3 (H-32) 25
Al(OH)3 (H-10) 50
melamine 1.9
ammonium polyphosphate 10
pentaerythritol 0.6
Short glass fiber 9.4
TABLE 5
weight (g)
Polyol (UR398A) 33.9
Dispersing agent 1.61
(2280)
Dispersing agent 0.86
(Disperbyk-110)
In the Comparative Examples 3-5, aluminum hydroxide of three different particle sizes (H-42M (1 μm), H-32 (8 μm), H-10 (55 μm)) were used individually. In each of the Comparative Examples, the additional amount of the aluminum hydroxide was maximized as much as possible (before incurring unprocessable high viscosity). Therefore, the additional amount of the smaller particle was less than that of the larger particle.
Comparative Example 3
The ingredients and amounts thereof given in Table 6 were thoroughly mixed to provide Liquid G. 60 g of H-42M was added to Liquid G and thoroughly mixed at a speed of 250 rpm for 7 minutes; thus, providing a first premixture. Meanwhile, 65 g of H-42M was added to 101.8 g of polyisocyanate (UR398B, Liquid B) and thoroughly mixed at a speed of 250 rpm for 7 minutes; thus, providing a second premixture. The first and second premixtures were mixed at a speed of 1200 rpm for about 10 seconds, and then placed into a mold to proceed with the foaming process. A 4 cm*10 cm*10 cm foam with a density of 0.31 g/cm3 was obtained. The fire retardant present in the foam was 41.8%.
TABLE 6
weight (g)
Polyol (UR398A) 67.8
Dispersing agent 3.22
(2280)
Dispersing agent 0.86
(Disperbyk-110)
Comparative Example 4
90 g of H-32 was added to the Liquid G as in the Comparative Example 3 and thoroughly mixed at a speed of 250 rpm for 7 minutes; thus, providing a first premixture. Meanwhile, 125 g of H-32 was added to 101.8 g of polyisocyanate (UR398B, Liquid B) and thoroughly mixed at a speed of 250 rpm for 7 minutes; thus, providing a second premixture. The first and second premixtures were mixed at a speed of 1200 rpm for about 10 seconds, and then placed into a mold to proceed with the foaming process. A 4 cm*10 cm*10 cm foam with a density of 0.32 g/cm3 was obtained. The fire retardant present in the foam was 55.3%.
Comparative Example 5
126 g of H-10 was added to the Liquid G as in the Comparative Example 3 and thoroughly mixed at a speed of 250 rpm for 7 minutes; thus, providing a first premixture. Meanwhile, 144 g of H-10 was added to 101.8 g of polyisocyanate (UR398B, Liquid B) and thoroughly mixed at a speed of 250 rpm for 7 minutes; thus, providing a second premixture. The first and second premixtures were mixed at a speed of 1200 rpm for about 10 seconds, and then placed into a mold to proceed with the foaming process. A 4 cm*10 cm*10 cm foam with a density of 0.34 g/cm3 was obtained. The fire retardant present in the foam was 60.8%.
A flame test was conducted on the foams obtained in the Comparative Examples 3-5 by a gas torch (burner diameter 1.5 inches) with a flame temperature of 950° C., during which the backside temperature of the foams was measured, wherein the results are shown in FIG. 9. All of the foams prepared by the Comparative Examples 3-5 cracked under the same flame test applied for the Example 1.
Accordingly, the invention provides a low-density, fire-resistant polyurethane foam which is capable of withstanding flame temperature of about 1000° C. for more than 1 hour without losing its structural integrity. The fire resistance is higher than that produced by the conventional fabrication schemes or by a single-particle-size fire retardant.
While the invention has been described by way of example and in terms of the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. To the contrary, it is intended to cover various modifications and similar arrangements (as would be apparent to those skilled in the art). Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements.

Claims (12)

What is claimed is:
1. A method for fabricating a fire-resistant polyurethane foam, comprising
premixing a polyisocyanate and a hydroxyl-containing inorganic fire retardant to form a first premixture, wherein the polyisocyanate reacts with the hydroxyl-containing inorganic fire retardant to form a chemical bond;
premixing a polyol, a blowing agent, and the hydroxyl-containing inorganic fire retardant to form a second premixture; and
mixing the first premixture and the second premixture to proceed with a foaming reaction to obtain a fire-resistant polyurethane foam,
wherein the hydroxyl-containing inorganic fire retardant comprises particles sizes of 0.5-5 μm, 5-20 μm, and 20-100 μm in a weight ratio of 1:0.1-2:0.1-2.
2. The method as claimed in claim 1, wherein the polyisocyanate has an NCO content of about 5-50 wt %.
3. The method as claimed in claim 1, wherein the polyisocyanate comprises toluene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′-dicyclohexylmethane diisocyanate (H12MDI), p-phenylene diisocyanate (PPDI), (p,p′-bisphenyl diisocyanate (BPDI), or combinations thereof.
4. The method as claimed in claim 1, wherein the polyol has two or more active groups and comprises polyether polyols, polyester polyols, or combinations thereof.
5. The method as claimed in claim 1, wherein the hydroxyl-containing inorganic fire retardant has the hydroxyl group either inherently or through a surface modification, and wherein the hydroxyl-containing inorganic fire retardant comprises aluminum hydroxide, magnesium hydroxide, silicon oxide, titanium oxide, calcium carbonate, or combinations thereof.
6. The method as claimed in claim 1, wherein the hydroxyl-containing inorganic fire retardant is present in an amount of about 50-80 wt %, based on the weight of the fire-resistant polyurethane foam.
7. The method as claimed in claim 1, wherein a weight ratio of the hydroxyl-containing inorganic fire retardant in the first premixture to the hydroxyl-containing inorganic fire retardant in the second premixture is about 1:9 to about 9:1.
8. The method as claimed in claim 1, wherein the second premixture further comprises a dispersing agent.
9. The method as claimed in claim 1, wherein the second premixture further comprises a catalyst.
10. The method as claimed in claim 1, wherein the fire-resistant polyurethane foam further comprises a phosphorus-containing fire retardant, a nitrogen-containing fire retardant, a carbonization agent, glass fiber, or combinations thereof.
11. The method as claimed in claim 1, wherein the fire-resistant polyurethane foam has a density of about 0.05-0.7 g/cm3.
12. The method as claimed in claim 1, wherein the fire-resistant polyurethane foam is capable of withstanding flame temperature of about 1000° C. for more than 1 hour.
US12/900,478 2009-11-20 2010-10-08 Fire-resistant polyurethane foam and fabrication method thereof Active 2031-04-21 US8604093B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US14/073,805 US8865782B2 (en) 2009-11-20 2013-11-06 Fire-resistant polyurethane foam

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
TW098139458A TWI394764B (en) 2009-11-20 2009-11-20 Fire-resistant polyurethane foam and fabrication method thereof
TW98139458A 2009-11-20
TW098139458 2009-11-20

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/073,805 Division US8865782B2 (en) 2009-11-20 2013-11-06 Fire-resistant polyurethane foam

Publications (2)

Publication Number Publication Date
US20110124760A1 US20110124760A1 (en) 2011-05-26
US8604093B2 true US8604093B2 (en) 2013-12-10

Family

ID=43302718

Family Applications (2)

Application Number Title Priority Date Filing Date
US12/900,478 Active 2031-04-21 US8604093B2 (en) 2009-11-20 2010-10-08 Fire-resistant polyurethane foam and fabrication method thereof
US14/073,805 Active US8865782B2 (en) 2009-11-20 2013-11-06 Fire-resistant polyurethane foam

Family Applications After (1)

Application Number Title Priority Date Filing Date
US14/073,805 Active US8865782B2 (en) 2009-11-20 2013-11-06 Fire-resistant polyurethane foam

Country Status (4)

Country Link
US (2) US8604093B2 (en)
EP (1) EP2336209B1 (en)
JP (1) JP6166011B2 (en)
TW (1) TWI394764B (en)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014520905A (en) * 2011-06-29 2014-08-25 ダウ グローバル テクノロジーズ エルエルシー Flame retardant composition, fiber reinforced polyurethane composite article containing flame retardant composition and use thereof
TWI477552B (en) * 2012-06-28 2015-03-21 Fire-resistant polyurethane material and fire-resistant structure
JP2014047251A (en) * 2012-08-30 2014-03-17 Mamoru Maeda Fireproof powder and foam type fire prevention composition containing the same
DE102012109500A1 (en) * 2012-10-05 2014-04-10 Dr. Neidlinger Holding Gmbh Heat-dissipating polymer and resin compositions for producing the same
TWI481664B (en) * 2012-12-14 2015-04-21 Ind Tech Res Inst Flexible non-combustible fire-resistant material
US9422394B2 (en) 2013-06-28 2016-08-23 Sabic Global Technologies B.V. Thermoplastic polyurethane and associated method and article
US9169368B2 (en) 2013-07-30 2015-10-27 Sabic Global Technologies B.V. Rigid foam and associated article
US9266997B2 (en) 2013-09-20 2016-02-23 Sabic Global Technologies B.V. Polyurethane foam and associated method and article
TWI504734B (en) 2013-12-31 2015-10-21 Ind Tech Res Inst Flame retardant composite material, plate and coating
JP5863934B1 (en) * 2014-11-21 2016-02-17 サンユレック株式会社 Polyurethane resin composition
JP6537300B2 (en) * 2015-03-03 2019-07-03 デンカ株式会社 Thermal insulation material and method of manufacturing the same
JP6567295B2 (en) * 2015-03-03 2019-08-28 デンカ株式会社 Insulating material and manufacturing method thereof
AU2016280609A1 (en) * 2015-06-18 2018-01-25 Dow Global Technologies Llc Viscoelastic polyurethane foam with aqueous polymer dispersant
CN106279629A (en) * 2016-08-25 2017-01-04 谢松芬 Nano-wear-resistant polyurethane external-wall heat-insulation material
CN107383310B (en) * 2017-07-24 2020-05-12 应瑶琪 Preparation method of phosphated flame-retardant polyurethane material
CN107325260A (en) * 2017-08-08 2017-11-07 桂林电子科技大学 A kind of modified phosphorus nitrogen expansion type combustion inhibitor fire-retardant polyurethane foam and preparation method
DE102018209444B3 (en) 2018-06-13 2019-07-25 Fresenius Medical Care Deutschland Gmbh Process for casting hollow-fiber membranes, hollow-fiber membrane filters and isocyanate group-containing adduct
CN108997549A (en) * 2018-06-27 2018-12-14 扬中市天正合成材料研究中心 The environmental protection flame retardant polyurethane foam material and preparation method tried to get to the heart of a matter for car fuel tank
JP2020037681A (en) * 2018-08-31 2020-03-12 株式会社エフコンサルタント Curable composition
CN109503792A (en) * 2018-11-08 2019-03-22 青岛正能交通装备有限公司 A kind of polyurethane foam standard EMU operation bench mask and preparation method thereof
WO2023036801A1 (en) 2021-09-07 2023-03-16 Basf Se Ionic monomer- based polyurethane foams and use thereof in trench breakers or pipeline pillows or thermally insulative material

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5130298A (en) 1974-09-09 1976-03-15 Mitsuboshi Belting Ltd
GB1472245A (en) 1975-06-16 1977-05-04 Gaf Corp Production of polyurethane foam materials
GB1499168A (en) 1976-11-01 1978-01-25 Hairlok Ltd Flame resistant foams
US4317889A (en) 1980-10-24 1982-03-02 Tenneco Chemicals, Inc. Intumescent flexible polyurethane foam
US4374207A (en) 1980-10-24 1983-02-15 G.F.C. Foam Corporation Intumescent flexible polyurethane foam
US4546117A (en) 1983-04-22 1985-10-08 Mobay Chemical Corporation Combustion modified flexible polyurethane foam
EP0308769B1 (en) 1987-09-24 1995-12-13 Metzeler Schaum Gmbh Process for preparing difficultly inflammable polyurethane foams
DE19726502C1 (en) 1997-06-23 1998-07-30 Peter Silbernagel Imitation stone slabs comprising polyurethane foam filled with natural or synthetic powdered stone
US6010565A (en) 1996-07-16 2000-01-04 Metallgesellschaft Aktiengesellschaft Foamed material for fireproofing and/or insulating
WO2000046283A1 (en) 1999-02-02 2000-08-10 The Dow Chemical Company Open-celled semi-rigid foams with exfoliating graphite
US20020052425A1 (en) * 1997-04-02 2002-05-02 Motonao Kaku Polyurethane foam, process for producing the same, and foam forming composition
US6706774B2 (en) * 2000-02-22 2004-03-16 Hilti Aktiengesellschaft Two-component on-site foam system and its use for foaming openings for the purpose of fire protection
TWI254729B (en) 1999-07-09 2006-05-11 Daihachi Chem Ind Flame retarder for resin and a flame retardant resin composition containing the same
US20080171805A1 (en) 2007-01-17 2008-07-17 Diego Mingarelli Waterproofing product that reduces the spread of fire

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2826906B2 (en) * 1994-04-08 1998-11-18 エコマット インコーポレイテッド Cured unsaturated polyester-polyurethane hybrid highly filled resin foam
JPH11269296A (en) * 1998-03-19 1999-10-05 Sanyo Chem Ind Ltd Preparation of inorganic organic composite foam

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5130298A (en) 1974-09-09 1976-03-15 Mitsuboshi Belting Ltd
GB1472245A (en) 1975-06-16 1977-05-04 Gaf Corp Production of polyurethane foam materials
GB1499168A (en) 1976-11-01 1978-01-25 Hairlok Ltd Flame resistant foams
US4317889A (en) 1980-10-24 1982-03-02 Tenneco Chemicals, Inc. Intumescent flexible polyurethane foam
US4374207A (en) 1980-10-24 1983-02-15 G.F.C. Foam Corporation Intumescent flexible polyurethane foam
CA1152698A (en) 1980-10-24 1983-08-23 Michael P. Pcolinsky, Jr. Intumescent flexible polyurethane foam
US4546117A (en) 1983-04-22 1985-10-08 Mobay Chemical Corporation Combustion modified flexible polyurethane foam
CA1222599A (en) 1983-04-22 1987-06-02 John F. Szabat Combustion modified flexible polyurethane foam
EP0308769B1 (en) 1987-09-24 1995-12-13 Metzeler Schaum Gmbh Process for preparing difficultly inflammable polyurethane foams
US6010565A (en) 1996-07-16 2000-01-04 Metallgesellschaft Aktiengesellschaft Foamed material for fireproofing and/or insulating
EP0912457B1 (en) 1996-07-16 2001-11-28 Chemetall GmbH Foamed material for fireproofing and/or insulating
US20020052425A1 (en) * 1997-04-02 2002-05-02 Motonao Kaku Polyurethane foam, process for producing the same, and foam forming composition
DE19726502C1 (en) 1997-06-23 1998-07-30 Peter Silbernagel Imitation stone slabs comprising polyurethane foam filled with natural or synthetic powdered stone
WO2000046283A1 (en) 1999-02-02 2000-08-10 The Dow Chemical Company Open-celled semi-rigid foams with exfoliating graphite
TWI254729B (en) 1999-07-09 2006-05-11 Daihachi Chem Ind Flame retarder for resin and a flame retardant resin composition containing the same
US6706774B2 (en) * 2000-02-22 2004-03-16 Hilti Aktiengesellschaft Two-component on-site foam system and its use for foaming openings for the purpose of fire protection
US20080171805A1 (en) 2007-01-17 2008-07-17 Diego Mingarelli Waterproofing product that reduces the spread of fire

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Notification of examination opinion issued by the Taiwan Intellectual Property Office on Nov. 28, 2012, for the above-referenced application's counterpart application in Taiwan (Application No. 098139458).
Office Action issued by the Japan Patent Office on Mar. 5, 2013, regarding the above-referenced application's counterpart application in Japan (Application No. 2010-260224).
Partial EPO Search Report, issued Jan. 31, 2011, for counterpart application filed with EPO (10013896.5).

Also Published As

Publication number Publication date
TWI394764B (en) 2013-05-01
JP6166011B2 (en) 2017-07-19
US20110124760A1 (en) 2011-05-26
JP2011105940A (en) 2011-06-02
EP2336209A2 (en) 2011-06-22
US8865782B2 (en) 2014-10-21
US20140058006A1 (en) 2014-02-27
EP2336209A3 (en) 2014-08-20
EP2336209B1 (en) 2017-09-20
TW201118108A (en) 2011-06-01

Similar Documents

Publication Publication Date Title
US8604093B2 (en) Fire-resistant polyurethane foam and fabrication method thereof
CN1840561B (en) Method for manufacturing hard polyurethane slabby foam and heat-insulating material for piping
BRPI0619772A2 (en) rigid polyurethane resin, flame retardant, water blown
JP4745778B2 (en) Polyisocyanurate foam and foam board using the same
EP1894955A1 (en) Rigid polyurethane foams with low thermal conductivity and a process for their production
JP4541970B2 (en) Polyisocyanurate foam and foam board using the same
CN102093531B (en) Fireproof polyurethane foamed material and preparation method thereof
KR101726700B1 (en) Thermoplastic polyurethane with cross-linking sites and Cross-linking foam method using the same
JP2013144397A (en) Fire resistant construction and method of manufacturing the same, and fire resistant composition
CN104619739B (en) Fire-retardant and/or antistatic, the polyurethane elastomer of non-mercury catalysis
JP4762614B2 (en) Low flammability polyurethane foam
BR0115467B1 (en) process for producing a low density rigid polyurethane foam, rigid polyurethane foam and thermal insulation board.
EP2743297A1 (en) Flexible non-combustible fire-resistant material
JP6839627B2 (en) Colored insulation board
JP4737967B2 (en) Polyurethane foam and method for producing the same
CA2048682A1 (en) Manufacturing method for ignition resistant polyisocyanurate foam
JP2009149760A (en) Production method for rigid polyurethane foam
US20080161437A1 (en) Novel polyisocyanurate foam materials containing CaCO3 filler
KR102055666B1 (en) Manufacturing method of semi-non-combustible hard polyurethane foam
KR102065251B1 (en) A manufacturing method of semi-inflammable insulation material
JP7163153B2 (en) colored insulation board
JP2000053742A (en) Isocyanurate-modified polyurethane foam and flame- retardant heat insulating panel
WO2024069787A1 (en) Urethane resin composition
KR101446339B1 (en) Rigid polyurethane foams for spray
JP2018009120A (en) Rigid urethane resin composition

Legal Events

Date Code Title Description
AS Assignment

Owner name: INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE, TAIWAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CHEN, PO-JU;JONG, SUNG-JENG;CHANG, REN-KUEN;AND OTHERS;SIGNING DATES FROM 20100923 TO 20100927;REEL/FRAME:025110/0752

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 8